Copolymerized polycarbonates

ABSTRACT

The present invention provides copolymerized copolyester-carbonates having improved flow and formability, in addition to excellent mechanical properties, heat resistance, transparency, and water resistance obtained by copolymerization of two or more aromatic dihydroxy compounds and a compound capable of reacting with those aromatic dihydroxy compounds to form carbonate linkages, characterized in that, of all the constituent repeating units derived from aromatic dihydroxy compounds, 2-40 mole % are derived from resorcin and/or substituted resorcins.

This is a divisional of application Ser. No. 08/119,317 filed on Sep. 9,1993 now U.S. Pat. No. 5,405,933, which is a continuation of Ser. No.07/863,926 filed on Apr. 6, 1992 which has been abandoned.

The present invention relates to copolymerized polycarbonates,specifically to copolymerized polycarbonates having improved formabilityand flow during forming, in addition to excellent mechanical properties,heat resistance, transparency, and water resistance.

Polycarbonates have excellent impact resistance and other mechanicalproperties as well as good heat resistance, transparency, etc. They arewidely used in various types of machine parts, optical disks, automobileparts, etc.

Conventional polycarbonates having such properties are usually producedby interfacial polymerization, in which bisphenol A reacts directly withphosgene.

Polycarbonates of this type have high glass transition temperatures(T_(g)). When they are melt formed into optical disks, etc., theirfluidity is increased by melting them at high temperatures.

Molded products of polymers in general, and polycarbonates inparticular, are more prone to show effects such as impaired transparencyand discoloration the longer the material remains in molten form at hightemperatures during molding. Thus, if the fluidity of polycarbonatesduring melt forming could be improved, the length of time they are keptin a molten state could be shortened, thus giving molded products whichare less affected by heat during forming. The forming characteristics ofthe polymers would also be improved in other respects, such as shortermolding cycle times and better productivity.

Thus there has been a demand for polycarbonates which show even betterflow and formability without sacrificing the inherent advantages ofpolycarbonates such as their mechanical properties, heat resistance, andtransparency.

As a result of determined research by the present inventors seeking toobtain polycarbonates with improved flow and formability without loss ofmechanical properties, heat resistance, water resistance, ortransparency, it has been found that copolymerized polycarbonates inwhich the constituent units formed from aromatic dihydroxy compoundscontain a certain proportion of units formed from resorcin and/orsubstituted resorcins show just such excellent properties. Thatdiscovery has led to the present invention.

The present invention has been developed with the above-mentionedproblems of the prior art in mind. Its object is to providecopolymerized polycarbonates having excellent mechanical properties,heat resistance, transparency, and water resistance, with improved flowand formability.

Copolymerized polycarbonates in accordance with the present inventionare formed by copolymerization of two or more aromatic dihydroxycompounds, and a compound capable of reacting with aromatic dihydroxycompounds to form carbonate linkages, and are characterized in that 2-40mole % of the constituent repeating units derived from aromaticdihydroxy compounds are derived from resorcin and/or substitutedresorcins.

Copolymerized polycarbonates in accordance with the present inventioncontain constituent units derived from resorcin and/or substitutedresorcins as a certain proportion of the constituent units derived fromaromatic dihydroxy compounds. They not only show excellent mechanicalproperties, heat resistance, and transparency, but also good waterresistance, and excellent melt flow and formability.

Copolymerized polycarbonates in accordance with the present inventionare explained below.

Copolymerized polycarbonates in accordance with the present inventionare obtained by copolymerization of two or more aromatic dihydroxycompounds with a compound capable of reacting with such dihydroxycompounds to form carbonate linkages. Among the constituent unitsderived from the aromatic dihydroxy compounds are constituent unitsderived from resorcin and/or substituted resorcins.

The constituent units derived from resorcin or substituted resorcins arerepresented by the following general formula I ##STR1##

In this formula [I], each R is a C₁₋₁₀ hydrocarbyl group or halogenatedhydrocarbyl group, or a halogen atom. n is an integer from 0 to 4. Whenn is 2 or more, the various R groups may be the same or different.

The resorcin or substituted resorcins referred to above may be resorcin,3-methylresorcin, 3-ethylresorcin, 3-propylresorcin, 3-butylresorcin,3-tert-butylresorcin, 3-phenylresorcin, 3-cumylresorcin,2,3,4,5-tetrafluororesorcin, 2,3,4,5-tetrabromoresorcin, etc.

Of the various compounds of this type, resorcin is preferred.

Copolymerized polycarbonates in accordance with the present inventionshould comprise 2-40 mole %, preferably 2-30 mole %, more preferably5-25 mole %, constituent units derived from resorcin or substitutedresorcins, where the total of all constituent units derived fromaromatic dihydroxy compounds is 100 mole %.

Such copolymerized polycarbonates containing 2-40 mole % constituentunits derived from resorcin and/or substituted resorcins show improvedflow and formability. If the proportion of constituent units fromresorcin and/or substituted resorcins exceeds 40 mole %, however, theheat resistance, water resistance, and thermal stability of the materialwill tend to be impaired.

There is no particular restriction on the constituent units derived fromaromatic dihydroxy compounds other than resorcin and/or substitutedresorcins; they may be formed from any of the following aromaticdihydroxy compounds commonly used to make polycarbonates. ##STR2##(where B is ##STR3## --O--, --S--, --SO-- or --SO₂ --, R¹ and R² arehydrogen atoms or monovalent hydrocarbyl groups, R³ is a divalenthydrocarbylene group, and R⁴ and R⁵ are halogen atoms or monovalenthydrocarbyl groups, each of which may be the same as or different fromthe others, and p and q are both integers from 0 to 4).

Examples of such aromatic dihydroxy compounds include:

bis(4-hydroxyphenyl)methane,

1,1-bis(4-hydroxyphenyl)ethane,

2,2-bis(4-hydroxyphenyl)propane,

2,2-bis(4-hydroxyphenyl)butane,

2,2-bis(4-hydroxyphenyl)octane,

bis(4-hydroxyphenyl)phenylmethane,

2,2-bis(4-hydroxy-1-methylphenyl)propane,

1,1-bis(4-hydroxy-tert-butylphenyl)propane,

2,2-bis(4-hydroxy-3-bromophenyl)propane, and other bis(hydroxy aryl)alkanes,

1,1-bis(4-hydroxyphenyl)cyclopentane,

1,1-bis(4-hydroxyphenyl)cyclohexane, and other bis(hydroxy aryl)cycloalkanes,

4,4'-dihydroxydiphenyl ether,

4,4'-dihydroxy-3,3'-dimethyldiphenyl ether, and other dihydroxy arylethers,

4,4'-dihydroxydiphenyl sulfide,

4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfide, and other dihydroxy diarylsulfides,

4,4'-dihydroxydiphenyl sulfoxide,

4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfoxide, and other dihydroxydiaryl sulfoxides, and

4,4'-dihydroxydiphenyl sulfone,

4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfone, and other dihydroxy diarylsulfones.

Of the various compounds of this type, 2,2-bis(4-hydroxyphenyl)propaneis preferred.

In the production of copolymerized polycarbonates in accordance with thepresent invention, the compounds which react with these dihydroxycompounds to form carbonate linkages may be carbonate diesters, carbonylhalides, etc.

Specific examples include:

diphenyl carbonate,

ditolyl carbonate,

bis(chlorophenyl) carbonate,

m-cresyl carbonate

dinaphthyl carbonate,

bis(diphenyl) carbonate,

diethyl carbonate,

dimethyl carbonate,

dibutyl carbonate,

dicyclohexyl carbonate, and other carbonate diesters, phosgene, andother carbonyl halides.

Of the various compounds of this type, diphenyl carbonate is preferred.

Copolymerized polycarbonates in accordance with the present inventionmay also contain constituent repeating units derived from dicarboxylicacids, dicarboxylic acid esters, or dicarboxylic acid halides. Suchconstituent repeating units are polyester-polycarbonate units.

Specific examples of dicarboxylic acids include terephthalic acid,isophthalic acid, sebacic acid, decanedioic acid, dodecanedioic acid,etc.

Specific examples of dicarboxylic acid esters include diphenyl sebacate,diphenyl terephthalate, diphenyl isophthalate, diphenyl decanedioate,diphenyl dodecanedioate, etc.

Specific examples of dicarboxylic acid halides include terephthaloylchloride, isophthaloyl chloride, sebacoyl chloride, decanedioylchloride, dodecanedioyl chloride, etc.

Such polyester-polycarbonate units may be present in proportions of upto 50 mole %, preferably not more than 30 mole %, in copolymerizedpolycarbonates in accordance with the present invention.

Copolymerized polycarbonates in accordance with the present inventionmay also contain constituent units derived from polyfunctional compoundshaving three or more functional groups per molecule, so long as thisdoes not interfere with the object of the invention. The amount of suchconstituent units present in the copolymerized polycarbonate is usuallynot more than 0.03 mole, preferably 0.001-0.02 mole, more preferably0.001-0.01 mole.

The polyfunctional compounds are preferably compounds having three ormore phenolic hydroxyl groups or carboxyl groups. It is particularlypreferred to use compounds having three or more phenolic hydroxylgroups, such as:

1,1,1-tris(4-hydroxyphenyl)ethane,

2,2',2"-tris(4-hydroxyphenyl)diisopropylbenzene,α-methyl-α,α',α'-tris(4-hydroxyphenyl)-1,4-diethylbenzene,

α,α',α"-tris(4-hydroxyphenyl)-1,3,5-triisopropylbenzene,

fluoroglycin,

4,6-dimethyl-2,4,6-tri(4-hydroxyphenyl)heptane-2,1,3,5-tri(4-hydroxyphenyl)benzene,

2,2-bis[4,4-(4,4'-dihydroxyphenyl)cyclohexyl]propane, trimellitic acid,

1,3,5-benzenetricarboxylic acid, pyromellitic acid, etc.

Preferred among these compounds are 1,1,1-tris-(4-hydroxyphenyl)ethane,α,α',α"-tris(4-hydroxyphenyl)-1,3,5-triisopropylbenzene, etc.

Such copolymerized polycarbonates in accordance with the presentinvention generally have glass transition temperatures (T_(g)) of100°-150° C., preferably 110°-135° C., and thermal decompositiontemperatures of 350°-380° C., preferably 360°-380° C.

They usually have melt flow rates (MFR) (measured by the JIS K 7210standard method, with temperature 300° C. and load 1.2 kg) of 5-100 g/10min, preferably 8-50 g/10 min.

copolymerized polycarbonates in accordance with the present inventionhave excellent melt flow and formability in addition to good mechanicalproperties, heat resistance, transparency, color tone, and weatherresistance.

Copolymerized polycarbonates in accordance with the present invention,containing a certain proportion of constituent units derived fromresorcin or substituted resorcins such as those mentioned above, alsoshow excellent stability during prolonged holdup in the molten state, aswell as good water resistance.

Because such copolymerized polycarbonates can be formed using shortermelt processing times, they can be used to make copolymerizedpolycarbonate products with excellent properties which show little or noeffects from the heat used in forming them, in addition to theadvantages of shorter molding cycle times and better productivity.

Products formed from these copolymerized polycarbonates also showexcellent color stability during prolonged use, and so they are wellsuited for use in optical applications such as sheets, lenses, compactdisks, etc., automobile parts and other outdoor applications, as well asapplications such as instrument housings, etc.

Copolymerized polycarbonates in accordance with the present inventionnot only have thermal decomposition temperatures as high as those ofordinary polycarbonates, but also show good chemical resistance,including to gasoline. They are thus suitable for molding intoautomobile engine parts.

As noted above, copolymerized polycarbonates in accordance with thepresent invention are produced using aromatic dihydroxy compoundsincluding resorcin and/or substituted resorcins, and compounds whichreact with such aromatic dihydroxy compounds to form carbonate linkages.There is no particular restriction on the process used to make them.They can be produced by interfacial or solution polymerization using acarbonyl halide such as phosgene as the compound that reacts with thearomatic dihydroxy compounds to form carbonate linkages, or they may beproduced using carbonate diesters by melt polymerization, solid-statepolymerization, etc.

Of these various processes, melt polymerization is preferred. Somedetails of this process are described below.

Melt polycondensation processes are particularly preferred because someimpairment of transparency or color tone may occur if aromatic dihydroxycompounds including resorcin and/or substituted resorcins are made toreact directly with phosgene to form a copolymerized polycarbonatehaving constituent units derived from resorcin and/or substitutedresorcins.

When copolymerized polycarbonates are produced by melt polymerization,aromatic dihydroxy compounds including resorcin and/or substitutedresorcins are used along with carbonate diesters.

The resorcin and/or substituted resorcins used in the present inventionare represented by the following general formula III ##STR4##

In this formula III, each R is a C₁₋₁₀ hydrocarbyl group or halogenatedhydrocarbyl group, or a halogen atom. n is an integer from 0 to 4. Whenn is 2 or more, the various R groups may be the same or different.

Specific examples of these substituted resorcins include compounds suchas those listed previously.

The resorcin and/or substituted resorcins used may be just one compound,or a combination of such compounds.

Of these various compounds, resorcin is preferably used.

The aromatic dihydroxy compounds used in the production of copolymerizedpolycarbonates in accordance with the present invention include 2-40mole %, preferably 2-30 mole %, more preferably 5-25 mole %, resorcinand/or substituted resorcins.

The proportion of the aromatic dihydroxy compounds other than resorcinand/or substituted resorcins is 98-60 mole %, preferably 98-70 mole %,more preferably 95-75 mole %.

There is no particular restriction on the type of aromatic dihydroxycompounds other than resorcin and/or substituted resorcins, althoughcompounds represented by the following general formula IV in which thephenyl rings are substituted with aliphatic groups or halogen atoms, arecommonly used. ##STR5## (where B is ##STR6## --O--, --S--, --SO-- or--SO₂ --, R¹ and R² are hydrogen atoms or monovalent hydrocarbyl groups,R³ is a divalent hydrocarbylene group, and R⁴ and R⁵ are halogen atomsor monovalent hydrocarbyl groups, each of which may be the same as ordifferent from the others, and p and q are both integers from 0 to 4).

Specific examples of such aromatic dihydroxy compounds include thoselisted previously.

Of those various compounds, 2,2-bis(4-hydroxyphenyl) propane ispreferably used.

Specific examples of carbonate esters which can be used include thoselisted previously.

Of those, diphenyl carbonate is preferably used.

In accordance with the present invention, the carbonate diesters mayalso contain up to 50 mole %, preferably not more than 30 mole %,dicarboxylic acids, dicarboxylic acid esters, or dicarboxylic acidhalides.

Specific examples of the dicarboxylic acids, dicarboxylic acid esters,or dicarboxylic acid halides which may be used include the compoundslisted previously.

In the production of polycarbonates in accordance with the presentinvention, the amount of such carbonate diesters used should be 1.0-1.30moles, preferably 1.01-1.20 moles, per mole of aromatic dihydroxycompounds.

It is also possible in the production of polycarbonates in accordancewith the present invention to use polyfunctional compounds having threeor more functional groups per molecule in addition to the aromaticdihydroxy compounds and carbonate diesters mentioned above.

Specific examples of the compounds which may be used include thoselisted previously.

When polyfunctional compounds are used, their amount is usually up to0.03 mole, preferably 0.001-0.02 mole, more preferably 0.001-0.01 mole,per mole of aromatic dihydroxy compounds.

In accordance with the present invention, the aromatic dihydroxycompounds containing resorcin and/or substituted resorcins, and thecarbonate diesters, are preferably made to undergo melt polycondensationin the presence of a catalyst comprising an alkali metal compound and/oran alkaline-earth metal compound (a).

Preferred examples of such an alkali metal compound and/oralkaline-earth metal compound (a) include salts of organic acids orinorganic acids, oxides, hydroxides, hydrides, alcoholates, etc.

Specifically, alkali metal compounds which may be used include sodiumhydroxide, potassium hydroxide, lithium hydroxide, sodium hydrogencarbonate, potassium hydrogen carbonate, lithium hydrogen carbonate,sodium carbonate, potassium carbonate, lithium carbonate, sodiumacetate, potassium acetate, lithium acetate, sodium stearate, potassiumstearate, lithium stearate, sodium borohydride, lithium borohydride,sodium phenylborate, sodium benzoate, potassium benzoate, lithiumbenzoate, disodium hydrogen phosphate, dipotassium hydrogen phosphate,dilithium hydrogen phosphate, bisphenol A disodium salt, bisphenol Adipotassium salt, bisphenol A dilithium salt, sodium phenolate,potassium phenolate, lithium phenolate, etc.

Specific alkaline-earth metal salts which may be used include calciumhydroxide, barium hydroxide, magnesium hydroxide, strontium hydroxide,calcium hydrogen carbonate, barium hydrogen carbonate, magnesiumhydrogen carbonate, strontium hydrogen carbonate, calcium carbonate,barium carbonate, magnesium carbonate, strontium carbonate, calciumacetate, barium acetate, magnesium acetate, strontium acetate, calciumstearate, barium stearate, magnesium stearate, strontium stearate, etc.

These compounds may be used singly or in combinations.

The amount of alkali metal compound and/or alkaline-earth metal compound(a) used is generally 1×10⁰⁻⁶ to 1×10⁻³ mole, preferably 1×10⁻⁷ to1×10⁻⁶ mole, more preferably 1×10⁻⁷ to 2.5×10⁻⁶ mole, per mole ofaromatic dihydroxy compounds.

If the amount of alkali metal compound and/or alkaline-earth metalcompound (a) used is 1×10⁻⁰ to 1×10⁻³ mole per mole of aromaticdihydroxy compounds, the basicity of those compounds can be weakened orcompletely neutralized by adding acidic compounds (described below) inamounts which serve to maintain high polymerization activity while notadversely affecting the properties of the resulting copolymerizedpolycarbonate. In this way one can obtain copolymerized polycarbonatehaving excellent color tone, heat resistance, water resistance, weatherresistance, and stability when kept in a molten state for long periodsof time.

The catalyst used in accordance with the present invention may be acombination of an alkali metal compound and/or alkaline-earth metalcompound (a), as described above, with a basic compound (b), and/or aborate compound (c).

Examples of such a basic compound (b) include nitrogen compounds whichare easily decomposed or volatilized at high temperatures. Specificcompounds of this type include the following.

Alkyl, aryl, and/or alkaryl group-containing ammonium hydroxides, suchas tetramethylammonium hydroxide (Me₄ NOH), tetraethylammonium hydroxide(Et₄ NO), tetrabutylammonium hydroxide (Bu₄ NOH),trimethylbenzylammonium hydroxide (φ-CH₂ (Me)₃ NOH), etc.,

tertiary amines, such as trimethylamine, triethylamine,dimethylbenzylamine, triphenylamine, etc.,

secondary amines represented by R₂ NH (where R is an alkyl group such asmethyl, ethyl, etc., or an aryl group such as phenyl, tolyl, etc.),

primary amines represented by RNH₂ (where R is as above),

imidazoles, such as 2-methylimidazole, 2-phenylimidazole, etc.,

ammonia, or basic salts such as tetramethylammonium borohydride (Me₄NBH₄), tetrabutylammonium borohydride (Bu₄ NBH₄), tetrabutylammoniumtetraphenylborate (Bu₄ NBPh₄), tetramethylammonium tetraphenylborate(Me₄ NBPh₄), etc.

Of these various compounds, tetraalkyl ammonium hydroxides, inparticular electronic-grade tetraalkyl ammonium hydroxides having lowimpurity metal contents, are preferably used.

Examples of borate compounds (c) include boric acid, and borate estersrepresented by the following general formula.

    B(OR).sub.n (OH).sub.3-n

where R is a methyl, ethyl, or other alkyl group, phenyl or other arylgroup, etc., and n is 1, 2, or 3.

Specific borate esters of this type include trimethyl borate, triethylborate, tributyl borate, trihexyl borate, triheptyl borate, triphenylborate, tritolyl borate, trinaphthyl borate, etc.

Preferred combinations for use as catalysts in accordance with thepresent invention include combinations of

(a) an alkali metal compound and/or alkaline-earth metal compound, and

(b) a nitrogen-containing basic compound.

The alkali metal compound and/or alkaline-earth metal compound (s)should be used in the amount specified above. The amount of thenitrogen-containing basic compound (b) should be 1×10⁻⁶ to 1×10-1 mole,preferably 1×10⁻⁶ to 1×10⁻² mole, per mole of aromatic dihydroxycompounds. If the amount of nitrogen-containing basic compound (b) usedis 1×10⁻⁶ to 1×10⁻¹ mole per mole of aromatic dihydroxy compounds, thetransesterification and polymerization reactions will proceed atadequate rates, and the resulting copolymerized polycarbonate will haveexcellent color tone, heat resistance, water resistance, etc.

The use of such a catalyst combination of an alkali metal compoundand/or alkaline-earth metal compound (a) and a nitrogen-containing basiccompound (b) makes it possible to produce high-molecular-weightcopolymerized polycarbonates having excellent transparency, heatresistance, and water resistance, and improved color tone, at highpolymerization activities.

In accordance with the present invention it is preferable to use acatalyst combination of

(a) an alkali metal compound and/or alkaline-earth metal compound, and

(c) boric acid or a borate ester, or a catalyst combination of

(a) an alkali metal compound and/or alkaline-earth metal compound,

(b) a nitrogen-containing basic compound, and

(c) boric acid or a borate ester.

In such a catalyst combination, the alkali metal compound and/oralkaline-earth metal compound (a), and the nitrogen-containing basiccompound (b), are preferably used in the amounts specified above.

The amount of boric acid or borate ester (c) used should be 1×10⁻⁶ to1×10⁻¹ mole,, preferably 1×10⁻⁷ to 1×10⁻² mole, more preferably 1×10⁻⁶to 1×10⁻⁴ mole, per mole of aromatic dihydroxy compounds.

If the amount of boric acid or borate ester (c) used is 1×10⁻⁰ to 1×10⁻¹mole per mole of aromatic dihydroxy compounds, one can obtain acopolymerized polycarbonate which does not tend to lose molecular weightafter heat aging, and shows excellent color tone, heat resistance, andwater resistance.

In particular, the use of catalysts comprising (a) alkali metalcompounds and/or alkaline-earth metal compounds, (b) nitrogen-containingbasic compounds, and (c) boric acid or borate esters, makes it possibleto produce high-molecular-weight copolymerized polycarbonates havingexcellent transparency, heat resistance, and water resistance, andimproved color tone, at high polymerization activities.

Using this sort of catalyst, the polycondensation reaction of carbonatediesters with aromatic dihydroxy compounds including resorcin and/orsubstituted resorcins can be carried out under conditions similar tothose used in known polycondensation reactions of carbonate diesterswith aromatic dihydroxy compounds.

Specifically, the aromatic dihydroxy compounds react with the carbonatediesters at atmospheric pressure and a temperature of 80°-250° C.preferably 100°-230° C., more preferably 120°-190° C., 0 to 5 hours,preferably 0 to 4 hours, more preferably 0 to 3 hours, after which thepressure in the reaction system is lowered and the temperature increasedas the reaction between aromatic dihydroxy compounds and carbonatediesters proceeds, eventually reaching a pressure of less than 5 mm Hg,preferably less than 1 mm Hg, and a temperature of 240°-320° C., causepolycondensation of the aromatic dihydroxy compounds with the carbonatediesters.

This polycondensation may be carried out continously or batchwise, in atank, tubular, or column reactor.

The copolymerized polycarbonate thus obtained generally has an intrinsicviscosity [η] of 0.2-1.2 dL/g, preferably 0.3-1.0 dL/g.

In accordance with the present invention, it is preferred to add anacidic compound and optionally an epoxy compound to the reactionproduct, i.e. the copolymerized polycarbonate, thus obtained.

The acidic compound may be a Lewis acid, a Broensted acid, or an esterof a sulfur-containing strong acid, so long as it is capable ofneutralizing the alkaline compound (alkali metal compound,alkaline-earth metal compound, etc.) used as the catalyst.

A Broensted acid used for this purpose should have a pK_(a) of less than5, preferably less than 3, in aqueous solution at 25° C.

Using an acidic compound having such a pK_(a) value is advantageousbecause it can neutralize the alkali metal or alkaline-earth metal usedas the catalyst, and thus stabilize the resulting copolymerizedpolycarbonate.

Specific examples of Lewis acids include:

boron compounds, such as zinc borate, boron phosphate, etc.,

borate esters, such as B(OCH₃)₃, B(OEt)₃, B(OPh)₃, etc.,

aluminum compounds, such as aluminum stearate, aluminum silicate, etc.,

zirconium compounds, such as zirconium carbonate, zirconium alkoxides,zirconium hydroxycarboxylates, etc.,

gallium compounds, such as gallium phosphide, gallium antimonide, etc.,

germanium compounds, such as germanium oxide, organic germaniumcompounds, etc.,

tin compounds such as tetra- and hexaorganotin compounds, PhOsn(Bu)₂OSn(Bu)₂ OPh, etc.,

antimony compounds, such as antimony oxide, alkyl antimony compounds,etc.,

bismuth compounds, such as bismuth oxide, alkyl bismuth compounds, etc.,

zinc compounds, such as (CH₃ COO)₂ Zn, zinc stearate, etc., and

titanium compounds, such as alkoxy titanium compounds, titanium oxide,etc.

(In the formulas above, Ph represents a phenyl group, Et an ethyl group,and Bu a butyl group.)

Specific examples of Broensted acids include:

phosphoric acid, phosphorous acid, hypophosphorous acid, pyrophosphoricacid, polyphosphoric acid, boric acid, hydrochloric acid, hydrobromicacid, sulfuric acid, sulfurous acid, adipic acid, azelaic acid,dodecanoic acid, L-ascorbic acid, asparaginic acid, benzoic acid, formicacid, acetic acid, citric acid, glutamic acid, salicylic acid, nicotinicacid, fumaric acid, maleic acid, oxalic acid, benzenesulfinic acid,toluenesulfinic acid, benzenesulfonic acid, p-toluenesulfonic acid,p-toluenesulfonic acid, trifluoromethanesulfonic acid,naphthalene-sulfonic acid, sulfonated polystyrene, methylacrylate-sulfonated styrene copolymers, other sulfonic acids, etc.

Esters of sulfur-containing acids which may be used include dimethylsulfate, diethyl sulfate, methyl, ethyl, butyl, octyl, or phenyl estersof p-toluenesulfonic acid, methyl, ethyl, butyl, or octyl esters ofbenzenesulfonic acid, and other such compounds whose acid groups have apK_(a) of less than 3.

Of these various acidic compounds, those containing sulfur, phosphorus,etc. are preferred. Acidic compounds containing sulfur are particularlypreferred.

The acidic compounds are added to the reaction product in amountssufficient to neutralize or weaken the effect of residual alkalinecompounds on the copolymerized polycarbonate. The amount could be, forexample, 0.01-500 moles, preferably 0.1-100 moles, more preferably0.1-50 moles, most preferably 0.5-30 moles, per mole of residual alkalimetal compound and/or alkaline-earth metal compound in the copolymerizedpolycarbonate.

In particular when the acidic compound is a Lewis acid or a Broenstedacid with a pK_(a) greater than 3, the amount used should be 0.01-500moles, preferably 0.1-50 moles, more preferably 0.1-30 moles. If theacidic compound is a Broensted acid with a pK_(a) of 3 or less, or anester of a sulfur-containing acid, the amount used should be 0.01-500moles, preferably 0.1-15 moles, more preferably 0.1-7 moles.

Epoxy compounds which may be used in accordance with the presentinvention are compounds having one or more epoxy groups per molecule.There is no particular restriction on the amount used, although it isgenerally 0.0001-0.2 wt. part, preferably 0.001-0.1 wt. part, per 100wt. parts of copolymerized polycarbonate in the reaction product.

Specific examples of such epoxy compounds include epoxidized soybeanoil, epoxidized linseed oil, phenyl glycidyl ether, allyl glycidylether, tert-butylphenyl glycidyl ether, 3,4-epoxycyclohexylmethyl3,4-epoxycyclohexanecarboxylate, 3,4-epoxy-6-methylcyclohexylmethyl3,4-epoxy-6-methylcyclohexanecarboxylate, 2,3-epoxycyclohexylmethyl3,4-epoxycyclohexanecarboxylate, 4-(3,4-epoxy-5-methylcyclohexyl)butyl3,4-epoxycyclohexanecarboxylate, 3,4-epoxycyclohexylethylene oxide,cyclohexylmethyl 3,4-epoxycyclohexanecarboxylate,3,4-epoxy-6-methylcyclohexylmethyl 6-methylcyclohexanecarboxylate,bisphenol A diglycidyl ether, tetrabromobisphenol A glycidyl ether,phthalic acid diglycidyl ester, hexahydrophthalic acid diglycidyl ester,bis-epoxycyclopentadienyl ether, bis-epoxyethylene glycol,bis-epoxycyclohexyl adipate, butadiene diepoxide, tetraphenylethyleneepoxide, octyl epoxytalate [sic], epoxidized polybutadiene,3,4-dimethyl-1,2-epoxycyclohexane, 3,5-dimethyl-1,2-epoxycyclohexane,3-methyl-5-tert-butyl-1,2-epoxycyclohexane, octadecyl2,2-dimethyl-3,4-epoxycyclohexanecarboxylate, n-butyl2,2-dimethyl-3,4-epoxycyclohexanecarboxylate, cyclohexyl2-methyl-3,4-epoxycyclohexanecarboxylate, n-butyl2-isopropyl-3,4-epoxy-5-methylcyclohexanecarboxylate, octadecyl3,4-epoxycyclohexanecarboxylate, 2-ethylhexyl3',4'-epoxycyclohexanecarboxylate, 4,6-dimethyl-2,3-epoxycyclohexyl3',4'-epoxycyclohexanecarboxylate, 4,5-epoxytetrahydrophthalicanhydride, 3-tert-butyl-4,5-epoxytetrahydrophthalic anhydride, diethyl4,5-epoxy-cis-1,2-cyclohexanedicarboxylate, di-n-butyl-3-tert-butyl4,5-epoxy-cis-1,2-cyclohexanedicarboxylate, etc. These compounds may beused singly or in combinations of two or more.

When acidic and epoxy compounds are added at the same time to thecopolymerized polycarbonate reaction product, any excess acidic compoundreacts with the epoxy compound and is neutralized, and one thus obtainsa copolymerized polycarbonate having excellent color tone, heatresistance, water resistance, etc.

In the method of producing copolymerized polycarbonates in accordancewith the present invention, there is no particular restriction on thetechnique used to add the acidic compound and optionally an epoxycompound to the polycarbonate obtained as the reaction product. Forexample, the acidic compound and optionally an epoxy compound may beadded to the copolymerized polycarbonate in the molten state and kneadedwith it, or the acidic compound and optionally an epoxy compound may beadded to a solution of the copolymerized polycarbonate and stirred.

Once the polycondensation reaction is complete, the acidic and epoxycompounds may be added to the molten copolymerized polycarbonatereaction product simultaneously or one after the other, either in thereactor or in an extruder, and then kneaded. It is also possible topelletize the copolymerized polycarbonate, and then feed the acidiccompound and optionally an epoxy compound along with the pellets to asingle-screw or twin-screw extruder to melt knead them with the polymer.Another method is to dissolve the copolymerized polycarbonate in asuitable solvent, such as methylene chloride, chloroform, toluene,tetrahydrofuran, etc., to prepare a solution, and then add the acidiccompound and optionally an epoxy compound to the solution eithersimultaneously or one after the other, and stir.

When an acidic compound and an epoxy compound are added separately tothe copolymerized polycarbonate, either the acidic compound or the epoxycompound may be added first.

In addition to such acidic compounds and epoxy compounds, it is alsopossible in accordance with the present invention to add the usual heatstabilizers, Tinuvin ultraviolet absorbers, mold release agents,antistatic agents, slip agents, antiblocking agents, lubricants,antifogging agents, dyes, pigments, natural oils, synthetic oils, waxes,organic fillers, inorganic fillers, etc. to the copolymerizedpolycarbonate in amounts which do not interfere with the object of thepresent invention.

Specific examples of such heat stabilizers include phenolic stabilizers,organic thio ether stabilizers, organic phosphite stabilizers, hinderedamine stabilizers, and epoxy stabilizers.

Phenolic stabilizers include, for example, n-octadecyl3-(4-hydroxy-3',5'-di-tert-butylphenyl)propionate,Tetrakis[methylene-3-(3',5'-di-tert-butyl-4-hydroxyphenyl)propionato]methane,1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane, distearyl(4-hydroxy-3-methyl-5-tert-butyl)benzylmalonate,4-hydroxymethyl-2,6-di-tert-butylphenol, etc. These may be used singlyor in combinations of two or more.

Thio ether stabilizers include, for example, dilauryl thiodipropionate,distearyl thiodipropionate, dimyristyl 3,3'-thiodipropionate, ditridecyl3,3'-thiodipropionate, pentaerythritol tetrakis(β-laurylthiopropionate),etc. These may be used singly or in combinations of two or more.

Phosphorus-containing stabilizers include, for example:

aryl alkyl phosphites such as bis(2,4-di-tert-butylphenyl)pentaerythrityl diphosphite, diphenyl decyl phosphite, diphenyl isooctylphosphite, phenyl isooctyl phosphite, 2-ethylhexyl diphenyl phosphite,etc.,

trialkyl phosphites such as trimethyl phosphite, triethyl phosphite,tributyl phosphite, trioctyl phosphite, trinonyl phosphite, tridecylphosphite, trioctadecyl phosphite, distearyl pentaerythrityldiphosphite, tris(2-chloroethyl) phosphite, tris(2,3-dichloropropyl)phosphite, etc.,

tricycloalkyl phosphites such as tricyclohexyl phosphite, etc.,

triaryl phosphites such as triphenyl phosphite, tricresyl phosphite,tris(ethylphenyl) phosphite, tris-(2,4-di-tert-butylphenyl) phosphite,tris(nonylphenyl) phosphite, tris(hydroxyphenyl) phosphite, etc.,

trialkyl phosphates such as trimethyl phosphate, triethyl phosphate,tributyl phosphate, trioctyl phosphate, tridecyl phosphate, trioctadecylphosphate, distearyl pentaerythrityl diphosphate, tris(2-chloroethyl)phosphate, tris(2,3-dichloropropyl) phosphate, etc.,

tricycloalkyl phosphates such as tricyclohexyl phosphate, etc., and

triaryl phosphates such as triphenyl phosphate, tricresyl phosphate,tris(nonylphenyl) phosphate, 2-ethylphenyl diphenyl phosphate, etc.These may be used singly or in combinations of two or more.

Hindered amine stabilizers include, for example,bis(2,2,6,6-tetramethyl-4-piperidinyl) sebacate,bis(1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate,1-[2-{3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyloxy}ethyl]-4-{3-(3,5-di-tert-butyl-4-hydroxyphenyl)-propionyloxy}-2,2,6,6-tetramethylpiperidine,8-benzyl-7,7,9,9-tetramethyl-3-octyl-1,2,3-triazaspiro.sup.[4,8]undecan-2,4-dione, 4-benzoyloxy-2,2,6,6-tetramethylpiperidine,bis(1,2,2,6,6-pentamethyl-4-piperidinyl)2-(3,5-di-tert-butyl-4-hydroxybenzyl)-2-n-butylmalonate,tetrakis(2,2,6,6-tetramethyl-4-piperidinyl)1,2,3,4-butanetetracarboxylate, etc. These may be used singly or incombinations of two or more.

The amount of such heat stabilizers used should generally be 0.001-5 wt.parts, preferably 0.005-0.5 wt. part, more preferably 0.01-0.3 wt. part,per 100 wt. parts of the copolymerized polycarbonate.

These heat stabilizers may be added either in solid or liquid form.

In order to reduce the number of times the copolymerized polycarbonatehas to be reheated, these heat stabilizers are preferably added whilethe copolymerized polycarbonate is still in molten form, anywhere fromthe final polymerization reactor to the point at which the product iscooled and pelletized. Because the copolymerized polycarbonate containsheat stabilizers, thermal decomposition of the polymer will be inhibitedduring subsequent reheating and processing, such as extrusion orpelletizing operations.

One can also add ultraviolet absorbers at the same time as the heatstabilizers. There is no particular restriction on the type ofultraviolet absorber used. It may be any of the common ultravioletabsorbers, such as a salicylate ultraviolet absorber, a benzophenoneultraviolet absorber, a benzotriazole ultraviolet absorber, acyanoacrylate ultraviolet absorber, etc.

Specific examples of salicylate ultraviolet absorbers include phenylsalicylate, p-tert-butylphenyl salicylate, etc.

Benzophenone ultraviolet absorbers include 2,4-di-hydroxybenzophenone,2-hydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone,2,2'-dihydroxy-4,4'-dimethoxybenzophenone,2-hydroxy-4-methoxy-2'-carboxybenzophenone,2-hydroxy-4-methoxy-5-sulfobenzophenone trihydrate,2-hydroxy-4-n-octoxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone,4-dodecyloxy-2-hydroxybenzophenone,bis(5-benzoyl-4-hydroxy-2-methoxyphenyl)methane,2-hydroxy-4-methoxybenzophenone-5-sulfonic acid, etc.

Examples of benzotriazole ultraviolet absorbers include2-(2'-hydroxy-5'-methylphenyl)benzotriazole,2-(2'-hydroxy-3',5'-di-tert-butylphenyl)benzotriazole,2-(2'-hydroxy-3'-tert-butyl-5'-methylphenyl)-5-chlorobenzotriazole,2-(2'-hydroxy-3',5'-di-tert-butylphenyl)-5-chlorobenzotriazole,2-(2'-hydroxy-5'-tert-octylphenyl)benzotriazole,2-(2'-hydroxy-3',5'-di-tert-amylphenyl)benzotriazole,2-[2'-hydroxy-3'-(3',4',5',6'-tetrahydrophthalimidomethyl)-5'-methylphenyl]benzotriazole,2,2'-methylenebis[4-(1,1,3,3-tetramethylbutyl)-6-(2H-benzotriazol-2-yl)phenol],etc.

Cyanoacrylate ultraviolet absorbers include 2-ethylhexyl2-cyano-3,3-diphenylacrylate, ethyl 2-cyano-3,3-diphenylacrylate, etc.They may be used singly or in combinations of two or more.

The amount of ultraviolet absorbers used is ordinarily 0.001-5 wt.parts, preferably 0.005-1 wt. part, more preferably 0.01-0.5 wt. part,per 100 wt. parts of the copolymerized polycarbonate.

In accordance with the present invention, mold release agents may alsobe added at the same time as the heat stabilizers described above. Thereis no particular restriction on the type of mold release agent used; itmay be any of the common mold release agents. Examples include:

hydrocarbon mold release agents, such as natural and syntheticparaffins, polyethylene waxes, fluorocarbons, etc.,

fatty acid mold release agents, such as stearic acid, hydroxystearicacid, other higher fatty acids, hydroxy fatty acids, etc.,

fatty amide mold release agents, such as stearamide,ethylenebisstearamide, other alkylene bis fatty amides, etc.,

alcohol mold release agents, such as stearyl alcohol, cetyl alcohol,other fatty alcohols, polyhydric alcohols, polyglycols, polyglycerols,etc.

fatty acid ester mold release agents, such as butyl stearate,pentaerythritol tetrastearate, other fatty acid esters of loweralcohols, fatty acid esters of polyhydric alcohols, fatty acid esters ofpolyglycols, etc., and

silicone mold release agents, such as silicone oils, etc.

These agents may be used singly or in combinations of two or more. Theamount of mold release agent used is ordinarily 0.001-5 wt. parts,preferably 0.005-1 wt. part, more preferably 0.01-0.5 wt. part, per 100wt. parts of the polycarbonate.

Colorants can also be added at the same time as the heat stabilizersdiscussed above. The colorants may be either pigments or dyes. Inorganicor organic colorants, or combinations of both types, can be used.

Specific examples of inorganic colorants include oxides such as titaniumdioxide and iron oxide red, hydroxides such as alumina white, sulfidessuch as zinc sulfide, selenides, ferrocyanides such as Prussian Blue,chromate salts such as zinc chromate and Molybden Red, sulfate saltssuch as barium sulfate, carbonate salts such as calcium carbonate,silicate salts such as ultramarine, phosphate salts such as ManganeseViolet, carbon in forms such as carbon black, metal powder pigments suchas bronze powder and aluminum powder, etc.

Specific examples of organic colorants include nitroso compounds such asNaphthol Green B, nitro compounds such as Naphthol Yellow S, azocompounds such as Resol Red, Bordeaux 10B, Naphthol Red, and CromophthalYellow, phthalocyanine compounds such as Phthalocyanine Blue and FastSky Blue, and condensed polycyclic colorants such as Indanthrone Blue,Quinacridone Violet, and Dioxazine Violet, etc.

These colorants may be used singly or in combinations of two or more.

The amount of such colorants used is ordinarily 1×10⁻⁶ to 5 wt. parts,preferably 1×10⁻⁶ to 3 wt. parts, more preferably 1×10⁻⁶ to 1 wt. part,per 100 wt. parts of the copolymerized polycarbonate.

In accordance with the present invention, the copolymerizedpolycarbonate obtained by the polycondensation reaction is preferablysubjected to a vacuum treatment following the addition of the acidiccompound and optionally an epoxy compound.

There is no particular restriction on the apparatus used for such vacuumtreatment. For example, one may use a reactor having a vacuum apparatusattached to it, or an extruder with a vacuum apparatus attached.

When a reactor is used, it may be a vertical tank reactor or ahorizontal tank reactor, although horizontal tank reactors arepreferred.

Vacuum treatment in such a reactor is performed at a pressure of0.05-750 mm Hg, preferably 0.05-5 mm Hg.

If vacuum treatment is carried out using an extruder, it is preferablyperformed for a period of approximately 10 seconds to 15 minutes. In areactor, on the other hand, the treatment time is preferably from about5 minutes to 3 hours. Vacuum treatment is preferably performed at atemperature of approximately 240°-350° C.

When vacuum treatment is carried out using an extruder, either a ventedsingle-screw extruder or a vented twin-screw extruder may be used. Thepolymer can also be pelletized at the same time.

When vacuum treatment is carried out in an extruder, it can be performedat a pressure of 1-750 mm Hg, preferably 5-700 mm Hg.

Thus, by adding an acidic compound and optionally an epoxy compound tothe copolymerized polycarbonate reaction product, then performing vacuumtreatment, one can obtain a copolymerized polycarbonate having lowerresidual monomer and oligomer contents.

Copolymerized polycarbonates obtained as described above contain arandom distribution of constituent units derived from the resorcinand/or substituted resorcins and carbonate diesters, and constituentunits derived from the other aromatic dihydroxy compounds and thecarbonate diesters.

Copolymerized polycarbonates in accordance with the present inventioncontain constituent units derived from resorcin and/or substitutedresorcins as a certain proportion of all the constituent units formedfrom aromatic dihydroxy compounds. Copolymerized polycarbonates of thistype have improved flow and formability in addition to excellentmechanical properties, heat resistance, transparency, and waterresistance.

The present invention will now be explained by means of some examples,although it is by no means limited to the examples described here.

The following test methods were used for property measurements:

    ______________________________________                                        Intrinsic Viscosity                                                                       measured with an Uberode                                          (IV) [dL/g]:                                                                              viscometer, in methylene chloride                                             solution at 20° C.                                         Melt Flow Rate                                                                            measured by the JIS K-7210 standard                               (MFR) [g/10 min]:                                                                         method, at 300° C. with a load                                         of 1.2 kg                                                         Color Tone (YI):                                                                          Test plates 3 mm thick were formed by                                         injection molding at cylinder temperature                                     290° C., injection pressure 1000 kg/cm.sup.2,                          cycle time 45 sec, and mold temperature                                       100° C. The X, Y and Z values for each                                 plate were measured by the transmission                                       method using a Color and Color Difference                                     Meter ND-1001 DP (from Nippon                                                 Denshoku Kogyo). The yellowness index                                         (YI) was obtained from the measured                                           values as follows.                                                            YI = 100 (1.277X - 1.060Z)/Y                                      Light Transmission:                                                                       measured by the ASTM D 1003 standard                                          method, using the same injection-molded test                                  plates as in the color tone measurements                          Haze:       measured with an NDH-200 meter (from                                          Nippon Denshoku Kogyo) using the same                                         injection-molded test plates as in the color                                  tone measurements                                                 Holdup Stability:                                                                         The resin was injection molded after                                          being held up in the molding machine at a                                     cylinder temperature of 320° C. for 15                                 minutes, and the YI and MFR of the result-                                    ing test plates were measured.                                    ______________________________________                                    

EXAMPLE 1

A charge of 0.450 mole of bisphenol A (from Nihon GE Plastics Ltd.),0.150 mole of resorcin (from Mitsui Sekiyu Kagaku Kogyo Ltd.), and 0.672mole diphenyl carbonate (from Enii Co.) was placed in a 500-mL glassreactor, blanketed with nitrogen, and heated to 180° C. with stirring bya nickel agitator for 30 minutes. Then 91.2 mg of a 15% aqueous solutionof tetramethyl-ammonium hydroxide (2.5×10⁻⁴ mole/mole bisphenol A) and19.2 mg of a 0.1% aqueous solution of sodium hydroxide (0.004×2.5×10⁻⁴mole/mole bisphenol A) were added, and the contents stirred for 30minutes to effect transesterification.

Then the temperature in the reactor was raised to 210° C. as thepressure was gradually lowered to 200 mm Hg and held at that value for 1hour, after which the temperature was raised to 240° C. (still at 200 mmHg) for 20 minutes, then the pressure was gradually lowered to 150 mm Hgand held for 20 minutes, then lowered to 150 mm Hg for 20 minutes, 100mm Hg for 20 minutes, and 15 mm Hg for 0.5 hour, after which thetemperature was raised to 270° C. and the pressure lowered to 0.5 mm Hgand the reaction allowed to continue for 2 hours.

After 2 hours the reactor was again blanketed with nitrogen, 5.472 mg ofa 5% toluene solution of butyl ρ-toluenesulfonate (0.008×2.5×10⁻⁴mole/mole bisphenol A) was added, and the reactor contents were stirredfor 30 minutes at 0.5 mm Hg, then formed into pellets.

The resulting copolymerized polycarbonate had an intrinsic viscosity(IV) of 0.49 dL/g).

The results are listed in Table 1.

EXAMPLES 2-5

The procedure in Example 1 was repeated using the amounts of bisphenol Aand resorcin shown in Table 1, and kneading the reaction product afterpolymerization with the compounds shown in Table 1, to obtaincopolymerized polycarbonates.

The results are listed in Table 1.

Comparison 1

The procedure in Example 1 was repeated using 0.600 mole of bisphenol A(from Nihon GE Plastics Ltd.) and no resorcin, to obtain apolycarbonate.

The results are shown in Table 1.

Comparison 2

The procedure in Comparison 1 was repeated using the type and amount ofheat stabilizer listed in Table 1, to obtain a polycarbonate.

The results are listed in Table 1.

Comparison 3

The properties of bisphenol A polycarbonate (Lexan LS2-111, from NihonGE Plastics Ltd.) are listed in Table 1.

Comparisons 4-5

The procedure in Example 1 was repeated, using 0.300 mole of bisphenol A(from Nihon GE Plastics Ltd.) and 0.300 mole of resorcin (from MitsuiSekiyu Kagaku Kogyo Ltd.), to obtain copolymerized polycarbonates.

The results are listed in Table 1.

Comparison 6

The procedure in Example 1 was repeated, using 0.300 mole of bisphenol A(from Nihon GE Plastics Ltd.), 0.300 mole of resorcin (from MitsuiSekiyu Kagaku Kogyo Ltd.), and 3.0 mg of a 3% aqueous solution of boricacid (0.1×2.5×10⁻⁴ mole/mole bisphenol A) to obtain a copolymerizedpolycarbonate. The intrinsic viscosity (IV) of the polymer was 0.48dL/g. The results are listed in Table 1.

                                      TABLE 1                                     __________________________________________________________________________                   Example 1                                                                            Example 2                                                                            Example 3                                                                            Example 4                                                                            Example 5                          __________________________________________________________________________    Bisphenol A/Resorcin                                                                         75/25  75/25  85/15  90/10  85/15                              (mole ratio in feed)                                                          Acidic         Butyl  Butyl  Butyl  Butyl  Butyl                              Compound       p-toluene-                                                                           p-toluene-                                                                           p-toluene-                                                                           p-toluene-                                                                           p-toluene-                         Added          sulfonate                                                                            sulfonate                                                                            sulfonate                                                                            sulfonate                                                                            sulfonate                          (moles/mole alkali metal)                                                                    2      2      2      2      2                                  Epoxy Compound 0      0,05   0      0      0.05                               Celloxide 2021P (Daicel)                                                      (g/100 g polymer)                                                             Additives                                                                     (g/100 g polymer)                                                             Irganox 168 (Ciba-Geigy)                                                                     0      0.05   0      0      0.05                               Mark A0-50 (Adeka-Argus)                                                                     0      0.05   0      0      0.05                               Cyasorb UV-5411 (Sun Chem)                                                                   0      0.3    0      0      0.3                                TSF 437 (Toshiba Silicone)                                                                   0      0.3    0      0      0.3                                Plast Violet 8840 (Bayer)                                                                    0      0.00006                                                                              0      0      0.00006                            Initial Properties                                                            Intrinsic Viscosity (dL/g)                                                                   0.49   0.49   0.49   0.49   0.49                               MFR (g/10 min) 15     16     13     12     14                                 Color Tone (YI)                                                                              2.0    0.6    1.9    1.8    0.6                                Light Transmission (%)                                                                       90.8   89.6   90.8   90.8   89.7                               Haze           0.3    0.3    0.4    0.3    0.3                                Holdup Stability                                                              MFR (g/10 min) 17     18     14     13     15                                 MFR Increase (%)                                                                             10     15     10     10     10                                 Color Tone (YI)                                                                              2.3    0.9    2.2    2.2    0.9                                Light Transmission (%)                                                                       90.7   89.6   90.7   90.7   90.1                               Heat Resistance HDT (°C.)                                                             123    123    130    131    130                                Heat Aging Resistance                                                                        37     13     36     35     12                                 Color Tone (YI)                                                               Water Resistance                                                                             2      4      1      1      4                                  Haze                                                                          __________________________________________________________________________                   Comp. 1                                                                             Comp. 2                                                                             Comp. 3                                                                            Comp. 4                                                                             Comp. 5                                                                             Comp. 6                           __________________________________________________________________________    Bisphenol A/Resorcin                                                                         100/0 100/0 Lexan                                                                              50/50 50/50 50/50                             (mole ratio in feed)       LS2                                                Acidic         Butyl Butyl --   Butyl Butyl --                                Compound       p-toluene-                                                                          p-toluene- p-toluene-                                                                          p-toluene-                              Added          sulfonate                                                                           sulfonate  sulfonate                                                                           sulfonate                               (moles/mole alkali metal)                                                                    2     2     --   2     2     --                                Epoxy Compound 0     0.05  --   0     0.05  0                                 Celloxide 2021P (Daicel)                                                      (g/100 g polymer)                                                             Additives                                                                     (g/100 g polymer)                                                             Irganox 168 (Ciba-Geigy)                                                                     0     0.05  --   0     0.05  0                                 Mark A0-50 (Adeka-Argus)                                                                     0     0.05  --   0     0.05  0                                 Cyasorb UV-5411 (Sun Chem)                                                                   0     0.3   --   0     0.3   0                                 TSF 437 (Toshiba Silicone)                                                                   0     0.3   --   0     0.3   0                                 Plast Violet 8840 (Bayer)                                                                    0     0.00006                                                                             --   0     0.00006                                                                             0                                 Initial Properties                                                            Intrinsic Viscosity (dL/g)                                                                   0.49  0.49  0.49 0.49  0.49  0.48                              MFR (g/10 min) 10    11    11   20    21    21                                Color Tone (YI)                                                                              1.8   0.6   0.5  2.1   0.7   2.0                               Light Transmission (%)                                                                       90.8  89.7  89.6 90.8  89.6  90.6                              Haze           0.3   0.3   0.4  0.4   0.4   0.4                               Holdup Stability                                                              MFR (g/10 min) 11    13    17   23    25    25                                MFR Increase (%)                                                                             5     15    55   15    20    20                                Color Tone (YI)                                                                              2.2   0.9   1.1  2.4   1.0   2.4                               Light Transmission (%)                                                                       90.4  90.3  90.3 90.7  89.6  90.4                              Heat Resistance HDT (°C.)                                                             135   135   135  111   111   110                               Heat Aging Resistance                                                                        35    11    27   44    28    52                                Color Tone (YI)                                                               Water Resistance                                                                             0.8   4     70   51    61    54                                Haze                                                                          __________________________________________________________________________

EXAMPLES 6-7

The procedure in Example 1 was repeated using the amounts of bisphenol Aand resorcin listed in Table 2 with a total polymerization time of 1.5hours, then the compounds listed in Table 2 were added in the amountsshown, and kneaded with the copolymerized polycarbonate, which was thenformed into pellets.

The polycarbonates had intrinsic viscosities (IV) of 0.42 dL/g. Theresults are listed in Table 2.

Comparison 7

The procedure in Example 1 was repeated using the amount of bisphenol Alisted in Table 2, with a total polymerization time of 1.5 hours, afterwhich the compounds listed in Table 2 were added in the amounts shownand kneaded with the copolymerized [sic] polycarbonate, which was thenformed into pellets.

The resulting copolymerized polycarbonate had an intrinsic viscosity(IV) of 0.42 dL/g. The results are listed in Table 2.

Comparison 8

The properties of a bisphenol A polycarbonate (High Flow Grade, fromNippon GE Plastics Ltd.) are listed in Table 2.

The following stabilizers were used, as indicated in Tables 1 and 2.

Irganox 168, from Ciba-Geigy

Mark AO-59, from Adeka-Argus

Cyasorb UV-5411, from Sun Chemical

TSF 437, from Toshiba Silicone

Plast Violet 8840, from Bayer

                  TABLE 2                                                         ______________________________________                                                                   Comp.     Comp.                                             Example 6                                                                             Example 7 7         8                                        ______________________________________                                        Bisphenol  85/15     90/10     100/0   100/0                                  A/Resorcin                                                                    (mole ratio in                                                                feed)                                                                         Acidic     Butyl     Butyl     Butyl   --                                     Compound   p-toluene-                                                                              p-toluene-                                                                              p-toluene-                                     Added      sulfonate sulfonate sulfonate                                      (moles/mole                                                                              2         2         2       --                                     alkali metal)                                                                 Epoxy Compound                                                                           0.05      0.05      0.05    --                                     Celloxide 2021P                                                               (Daicel)                                                                      (g/100 g polymer)                                                             Additives                                                                     (g/100 g polymer)                                                             Irganox 168                                                                              0.05      0.05      0.05    --                                     (Ciba-Geigy)                                                                  Mark A0-50 0.05      0.05      0.05    --                                     (Adeka-Argus)                                                                 Cyasorb UV-5411                                                                          0.3       0.3       0.3     --                                     (Sun Chem)                                                                    TSF 437 (Toshiba                                                                         0.3       0.3       0.3     --                                     Silicone)                                                                     Plast Violet 8840                                                                        0.00006   0.00006   0.00006 --                                     (Bayer)                                                                       Initial Properties                                                            Intrinsic Viscosity                                                                      0.42      0.42      0.42    0.42                                   (dL/g)                                                                        MFR (g/10 min)                                                                           37        32        27      27                                     Color Tone (YI)                                                                          0.6       0.6       0.6     0.6                                    Light Trans-                                                                             89.7      89.7      89.7    89.7                                   mission (%)                                                                   Haze       0.3       0.3       0.3     0.3                                    Holdup Stability                                                              MFR (g/10 min)                                                                           41        35        31      34                                     MFR Increase                                                                             10        10        15      25                                     (%)                                                                           Color Tone (YI)                                                                          0.9       0.9       0.9     1.2                                    Light Trans-                                                                             90.1      90.1      90.4    90.3                                   mission (%)                                                                   Heat Resistance                                                                          130       131       132     132                                    HDT (°C.)                                                              Heat Aging 11        11        11      28                                     Resistance                                                                    Color Tone (YI)                                                               Water Resistance                                                                         4         4         4       80                                     Haze                                                                          ______________________________________                                    

We claim:
 1. A copolymerized polyester-polycarbonate consistingessentially of (a) units of the formula ##STR7## where B is ##STR8##--O--, --S--, --SO-- or --SO₂ --, R¹ and R² are hydrogen atoms ormonovalent hydrocarbyl groups, R³ is a divalent hydrocarbylene group,and (b) units of the formula ##STR9## where each R is a C₁₋₁₀hydrocarbyl group, a halogenated hydrocarbyl group, or a halogen atomand n is an integer from 0 to 4 provided that when n is 2 or more, the Rgroups are the same or different and (c) a group comprising units of theformula ##STR10## wherein up to 50 mol % of the units (c) are derivedfrom the group consisting of dicarboxylic acids, dicarboxylic acidesters, dicarboxylic acid halides or mixtures thereof whereby thecopolymerized polyester-polycarbonate has an intrinsic viscosity of from0.2 to 1.2 dL/g when measured at 20° C. in methylene chloride solution.2. The copolymerized polyester polycarbonate of claim 1 wherein (b)units constitute from 2 to 40 mole percent of the copolymerizedpolycarbonate.
 3. The copolymerized polyester polycarbonate of claim 1wherein (b) units constitute from 2 to 30 mole percent of thecopolymerized polycarbonate.
 4. The copolymerized polyesterpolycarbonate of claim 1 wherein (b) units constitute from 2 to 25 molepercent of the copolymerized polycarbonate.
 5. The copolymerizedpolyester polycarbonate of claim 1 wherein B in the formula for units(a) represents a group with the following formula: ##STR11##
 6. Thecopolymerized polyester polycarbonate of claim 1 wherein the intrinsicviscosity is from 0.3 to 1.0 dL/g.